US5608004A - Water base coating composition - Google Patents
Water base coating composition Download PDFInfo
- Publication number
- US5608004A US5608004A US08/416,983 US41698395A US5608004A US 5608004 A US5608004 A US 5608004A US 41698395 A US41698395 A US 41698395A US 5608004 A US5608004 A US 5608004A
- Authority
- US
- United States
- Prior art keywords
- water
- coating composition
- base coating
- water base
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920001225 polyester resin Polymers 0.000 claims abstract description 34
- 239000004645 polyester resin Substances 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 21
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- 239000004640 Melamine resin Substances 0.000 claims abstract description 19
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000011877 solvent mixture Substances 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 42
- 239000004593 Epoxy Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000002966 varnish Substances 0.000 description 21
- 238000001723 curing Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- 229920001807 Urea-formaldehyde Polymers 0.000 description 7
- 230000005856 abnormality Effects 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-RNGGSSJXSA-N (1r,2r,3s,4s)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@@H]2C=C[C@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-RNGGSSJXSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- CTJFNNZDSZIGOM-UHFFFAOYSA-N 3-methylcyclohex-2-ene-1,1,2-tricarboxylic acid Chemical compound CC1=C(C(O)=O)C(C(O)=O)(C(O)=O)CCC1 CTJFNNZDSZIGOM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VJQGGZWPOMJLTP-UHFFFAOYSA-N octadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCC(O)O VJQGGZWPOMJLTP-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to a high solid thermosetting water base coating composition having a low VOC (volatile organic compounds) value excellent in water resistance and hot water resistance, which is suitable as a coating agent for a metal substrate, particularly for an aluminum substrate.
- VOC volatile organic compounds
- water base coating agents employing a binder prepared by incorporating a large amount of carboxyl groups in a resin and then neutralizing them with a neutralizing agent (for example, International Patent Publication No. W088/03159, and Japanese Unexamined Patent Publications No. 52370/1983, No. 255766/1992, No. 342780/1992 and No. 370171/1992) and water base coating agents employing, as a binder, a resin obtained by emulsion polymerization of a monomer in water in the presence of an emulsifier, a dispersant or the like (for example, Japanese Examined Patent Publications No. 47281/1985 and No. 32230/1987 and Japanese Unexamined Patent Publications No. 265905/1988, No. 146967/1989 and No. 43830/1993) are mainly employed.
- a neutralizing agent for example, International Patent Publication No. W088/03159, and Japanese Unexamined Patent Publications No. 52370/1983, No. 255766
- the present invention has been made to overcome such drawbacks of conventional water base coating agents. It is an object of the present invention to provide a high solid thermosetting water base coating composition capable of forming a coating film excellent in the water resistance and hot water resistance, which brings about no or little pollution.
- the present inventors have conducted an extensive research to overcome the drawbacks of the conventional water base coating agents and as a result, have found that by using a certain specific binder component and a solvent mixture comprising water and a hydrophilic organic solvent, such a binder can be dissolved or dispersed stably in the solvent without using a neutralizing agent, an emulsifier or the like, and it is possible to obtain a high solid water base coating agent having a low VOC value, and further that the coating film thereby obtained is excellent in the water resistance and hot water resistance.
- the present invention has been accomplished on the basis of these discoveries.
- the present invention provides a water base coating composition having a solid content of from 50 to 80 wt % and having a binder component dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
- the present invention provides a water base coating composition having a pH of from 6 to 10 and a solid content of from 50 to 80 wt % and having a binder component and an epoxy phosphoric acid ester resin curing accelerator dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
- the binder component constituting the water base coating composition of the first aspect of the present invention comprises a polyester resin and, as a crosslinking agent, a melamine resin and/or a benzoguanamine resin.
- This polyester resin is the one which can be obtained by polycondensing a polybasic carboxylic acid or its acid anhydride with a polyhydric alcohol in accordance with a conventional method.
- an aromatic polybasic carboxylic acid or a polybasic carboxylic acid comprising an aromatic polybasic carboxylic acid as the main component (more than 80 mol %), or its acid anhydride is used in the present invention, so that the water resistance of the resulting coating film will be good.
- phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid or pyromellitic acid, and their anhydrides may be mentioned as typical examples.
- an aliphatic or alicyclic polybasic carboxylic acid or its acid anhydride such as adipic acid, succinic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, methylcyclohexene tricarboxylic acid, himic acid or cyclohexanedicarboxylic acid, or an anhydride thereof, may be used in combination with an aromatic polybasic carboxylic acid or its acid anhydride, in an amount of less than 20 mol %, preferably not more than 10 mol %, of the total polybasic carboxylic acid or its acid anhydride component.
- a monocarboxylic acid such as benzoic acid may be incorporated in an amount of less than 2 mol % of the total polybasic carboxylic acid or its acid anhydride component.
- a usual alcohol component for polyester such as ethylene glycol, diethylene glycol, propanediol, neopentyl glycol, triethylene glycol, dipropylene glycol, butylene glycol, hexanediol, trimethylol propane, glycerol, sorbitol, pentanediol, octadecanediol or pentaerythritol may be used without any particular restriction.
- Glycidyl esters or glycidyl ethers may be used in combination with the polyhydric alcohol for modification.
- the hydroxyl value is from 100 to 280, preferably from 120 to 250, and the acid value is from 0 to 15, preferably not higher than 10. Further, the weight average molecular weight is usually from 500 to 30,000, preferably from 1,000 to 10,000. If the hydroxyl value is lower than the above range, the affinity to water tends to be small, and the storage stability of the composition tends to be poor. Accordingly, a larger amount of an organic solvent is required. Further, crosslinking tends to be less during the curing, whereby the hardness or toughness of the coating film tends to be low.
- the hydroxyl value is higher than the above range, the flexibility of the resulting coating film tends to be poor. Further, if the acid value is higher than the above range, the viscosity of the composition tends to be high, and the water resistance of the coating film thereby obtained tends to be low, such being undesirable.
- a melamine resin having a triazine ring or a benzoguanamine resin having a triazine ring and an aromatic ring is used as a crosslinking agent to improve the water resistance and hot water resistance of the coating film thereby obtained.
- an alkyl-etherified melamine resin, an alkyl-etherified benzoguanamine resin, or an alkyl-etherified resin of diguanamine having two triazine rings bonded to a phenylene nucleus may be mentioned as a typical example.
- a benzoguanamine resin having an aromatic ring and a triazine ring is particularly preferred.
- a urea resin which is also an amino plasto resin does not have a triazine ring and accordingly is inferior in the water resistance or hot water resistance, and it is not advisable to incorporate such a urea resin in a large amount. However, it is possible to incorporate such a urea resin in an amount of up to 15 wt % in the total crosslinking agent.
- the binder component in the present invention comprises the polyester resin and the crosslinking agent, as described above.
- the blend ratio of the two is usually from 30:70 to 95:5, preferably from 40:60 to 80:20, as the weight ratio of the polyester resin to the crosslinking agent. If the polyester resin is less than this range, the crosslinking agent tends to react by itself, whereby the flexibility, chemical resistance, etc. of the coating film tend to deteriorate. On the other hand, if it is more than the above range, the crosslinking density tends to be low, whereby the water resistance, the hot water resistance, the solvent resistance, etc. tend to be low.
- binder component other resin such as an epoxy resin, a xylene resin or an acrylic resin may be used in combination as a part of the component.
- a solvent mixture comprising water and a hydrophilic organic solvent
- the hydrophilic organic solvent may, for example, be a solvent which is freely soluble in water at room temperature, such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, ethylene glycol, acetone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol or diethylene glycol monoethyl ether, or a solvent which is soluble in water at room temperature to some extent, such as sec-butanol, methyl ethyl ketone, ethyl formate, methyl acetate or propylene glycol monomethyl ether acetate.
- Such solvents may be used alone or in combination as a mixture of two or more of them.
- a hydrophilic organic solvent such as mineral spirit, toluene or xylene may be incorporated.
- the blend ratio of the water and the hydrophilic organic solvent varies depending upon the solid content of the water base coating composition, the hydroxyl value of the polyester resin, etc.
- the weight ratio of the water to the hydrophilic organic solvent is usually from 15:85 to 70:30, preferably from 20:80 to 55:45. If the amount of the organic solvent is less than this range, the storage stability under a high solid condition as an object of the present invention tends to be low. On the other hand, if it is more than the above range, the VOC value tends to be high, such being undesirable from the viewpoint of prevention of atmospheric pollution or conservation of resources.
- the water base coating composition according to the first aspect of the present invention comprises the above described binder component and the solvent mixture as essential components, and may further contain various additives including a pigment such as a coloring pigment or an extender pigment, an acidic catalyst, a leveling agent, a defoaming and a lubricant, as the case requires.
- the composition comprises from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight, of the pigment and from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of the additives, per 100 parts by weight of the binder component.
- the solvent mixture is incorporated so that the solid content of the water base coating composition would be from 50 to 80 wt %.
- the present invention provides a water base coating composition having a pH of 6 to 10 and a solid content of from 50 to 80 wt % and having an epoxy phosphoric acid ester curing accelerator incorporated to the water base coating composition according to the first aspect of the present invention which comprises the above-mentioned binder component and the solvent mixture as the essential components and which may contain a pigment or additives, as the case requires.
- the curing accelerator constituting the water base coating composition of the present invention can be produced, for example, by the following method. Namely, a phosphoric acid component such as orthophosphoric acid, a phosphoric acid condensate or pyrophosphoric acid is heat-reacted to an epoxy resin which preferably has an epoxy equivalent of from about 175 to 10,000, in the presence of a catalyst such as an imidazole or a phosphonium salt for triesterification or diesterification, followed by hydrolysis to obtain a monoesterified epoxy phosphoric acid ester resin curing accelerator.
- a phosphoric acid component such as orthophosphoric acid, a phosphoric acid condensate or pyrophosphoric acid
- an epoxy resin which preferably has an epoxy equivalent of from about 175 to 10,000
- a catalyst such as an imidazole or a phosphonium salt for triesterification or diesterification
- Such a curing accelerator has a hydroxyl group and a phosphoric acid residue in its molecule and thus accelerate curing of the coating film and at the same time reacts with the binder to provide excellent crosslinking accelerating effects. Yet, it contributes to improvement of the adhesion and the corrosion resistance.
- the water base coating composition according to the second aspect of the present invention is required to have a pH of from 6 to 10, preferably a pH of from 7 to 9, so that the above-mentioned epoxy phosphoric acid ester resin curing accelerator is stably dissolved in the composition.
- a neutralizing agent an amine compound such as methylamine, diethylamine, trimethylamine, triethylamine, cyclohexylamine, diaminobenzene, ethylenimine, ethanolamine, dimethylethanolamine or diethanolamine, or ammonia may be used as a typical example.
- the water base coating composition according to the second aspect of the present invention comprises from 1 to 30 parts by weight, preferably from 5 to 20 parts by weight of the curing accelerator, from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight, of the pigment and from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of the additives, per 100 parts by weight of the above described binder component. Further, the solvent mixture is incorporated so that the solid content of the water base coating composition would be from 50 to 80 wt %.
- the water base coating composition of the present invention is coated or printed on a substrate of a metal such as aluminum, stainless steel or steel, particularly preferably on an aluminum substrate, by a coating method such as roll coating, flow coating, spray coating or dip coating, or by a printing method such as gravure printing or screen printing, so that the dried film thickness would be from about 1 to 200 ⁇ m, preferably from 2 to 100 ⁇ m.
- the coating film can be cured within a wide range of baking conditions ranging from baking at a temperature of from 100° to 200° C. for from 1 to 30 minutes to baking at a temperature of from 220° to 250° C. for a short period of time of a few tens seconds.
- curing of the coating film is preferably conducted by baking at a temperature of from 150° to 200° C. for a short period of time of a few tens seconds, but it is possible to conduct baking at a baking temperature of not higher than 150° C. for a few minutes.
- the water base coating composition of the present invention does not require neutralization of a resin of a high acid value with a neutralizing agent as required by a conventional water base coating composition and does not use an emulsifier or the like. Further, it uses an aromatic polybasic carboxylic acid as the acid component of the polyester resin and uses a crosslinking agent having a triazine ring, whereby the film thereby obtained is excellent in water resistance and hot water resistance. Further, it has a low VOC value and a high solid content, whereby it contributes to prevention of atmospheric pollution or conservation of resources. Further, its water content is little and thus has a feature that bubbling scarcely forms as compared with a conventional water base coating agent.
- the composition will be excellent in low temperature curing in a short period of time without bringing about deterioration of the storage stability such as a viscosity increase, in addition to the above effects.
- Each water base coating composition thus obtained was coated on a chromate-treated aluminum plate (thickness: 0.2 mm) by a roll coater so that the dried film thickness would be 8 ⁇ m, then set for 5 seconds and thereafter baked at 225° C. for 90 seconds. With respect to the coated plate thus obtained, tests for the hardness, the water resistance and the impact resistance were conducted, and the results are shown in Table 3.
- water-soluble polyester varnish is "Water Sol S199-iM” (manufactured by Dainippon Ink and Chemicals, Inc.), solid content: 59%; "melamine resin (A)” is “Sumimal MC-1” (manufactured by Sumitomo Chemical Co., Ltd.), solid content 78%; “melamine resin (B)” is “Sumimal M40W” (manufactured by Sumitomo Chemical Co., Ltd.), solid content: 80%; “melamine resin (C)” is "Cymel 325" (manufactured by Mitsui Cyanamid K.
- VOC value i.e. the amount of the volatile organic solvent in the coating material, is the value calculated by the following formula: ##EQU1## where, V, volatile content (wt %) in the coating material V W : water content (wt %) in the coating material
- DH 2 O density of water (25° C., 0.997 g/ml)
- Pigm hardness is the value measured in accordance with JIS K5400; "water resistance” is the visual evaluation of the appearance of the coating film after immersion; “impact resistance” is tested by a Dupont system (1/2 ⁇ 300 gr ⁇ 20 cm) and evaluated by O: no abnormality and X: abnormality such as cracking or peeling occurred; and "appearance of the coating film” is the visual evaluation of the appearance of the coating film and represented by O: no abnormality and X: bubbles observed.
- Comparative Examples 1 to 6 wherein no epoxy phosphoric acid ester resin curing accelerator was employed and Comparative Examples 7 to 12 wherein an epoxy phosphoric acid ester resin curing accelerator was employed
- Comparative Examples 1 and 7 wherein a polyester resin having a large hydroxyl value was used, hot water resistance and the impact resistance were poor.
- Comparative Examples 2 and 8 wherein a polyester resin having a small hydroxyl value was used, a large amount of an organic solvent was required to secure the stability of the coating material, whereby the VOC value tended to be high, and the hot water resistance was poor.
- Comparative Examples 3 and 9 wherein an aliphatic polybasic carboxylic acid was used excessively, the hardness in hot water was low, the coating was susceptible to scratching.
- Comparative Examples 4 and 10 wherein a polyester resin having a large acid value was used, the hot water resistance was poor.
- Comparative Examples 5 and 11 wherein a urea resin was used as a crosslinking agent, the hot water resistance was poor.
- Comparative Examples 6 and 12 wherein the amount of water was substantial as conventional water base coating compositions, bubbles were formed in the coating films when the setting time was short.
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Abstract
A water base coating composition having a solid content of from 50 to 80 wt % and having a binder component dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
Description
The present invention relates to a high solid thermosetting water base coating composition having a low VOC (volatile organic compounds) value excellent in water resistance and hot water resistance, which is suitable as a coating agent for a metal substrate, particularly for an aluminum substrate.
In recent years, conversion from conventional organic solvent type coating agents to water base coating agents employing, as a solvent, water or a combination of water and an organic solvent, has been rapidly progressed from the viewpoint of prevention of atmospheric pollution, conservation of resources or the like.
As such water base coating agents, water base coating agents employing a binder prepared by incorporating a large amount of carboxyl groups in a resin and then neutralizing them with a neutralizing agent (for example, International Patent Publication No. W088/03159, and Japanese Unexamined Patent Publications No. 52370/1983, No. 255766/1992, No. 342780/1992 and No. 370171/1992) and water base coating agents employing, as a binder, a resin obtained by emulsion polymerization of a monomer in water in the presence of an emulsifier, a dispersant or the like (for example, Japanese Examined Patent Publications No. 47281/1985 and No. 32230/1987 and Japanese Unexamined Patent Publications No. 265905/1988, No. 146967/1989 and No. 43830/1993) are mainly employed.
However, such conventional water base coating agents have problems that the coating films thereby obtained are poor in the water resistance and hot water resistance, since they contain a large amount of carboxyl groups in the resin, or they contain an emulsifier or a dispersant. They also have a problem that the solid content is low i.e. the amount of water is substantial, whereby unless the coated or printed coating agents are sufficiently set and baked, the coating films are likely to have bubbling.
The present invention has been made to overcome such drawbacks of conventional water base coating agents. It is an object of the present invention to provide a high solid thermosetting water base coating composition capable of forming a coating film excellent in the water resistance and hot water resistance, which brings about no or little pollution.
The present inventors have conducted an extensive research to overcome the drawbacks of the conventional water base coating agents and as a result, have found that by using a certain specific binder component and a solvent mixture comprising water and a hydrophilic organic solvent, such a binder can be dissolved or dispersed stably in the solvent without using a neutralizing agent, an emulsifier or the like, and it is possible to obtain a high solid water base coating agent having a low VOC value, and further that the coating film thereby obtained is excellent in the water resistance and hot water resistance. The present invention has been accomplished on the basis of these discoveries. Further, it has been found that by incorporating a certain specific curing accelerator to the water base coating agent, curing can be carried out at a low temperature within a short period of time without deterioration of the storage stability such as the viscosity increase, and the coating film thereby obtained has improved adhesion and corrosion resistance. A second aspect of the present invention has been accomplished on the basis of these discoveries.
Thus, according to the first aspect, the present invention provides a water base coating composition having a solid content of from 50 to 80 wt % and having a binder component dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
According to the second aspect, the present invention provides a water base coating composition having a pH of from 6 to 10 and a solid content of from 50 to 80 wt % and having a binder component and an epoxy phosphoric acid ester resin curing accelerator dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
Now, the present invention will be described in detail.
The binder component constituting the water base coating composition of the first aspect of the present invention, comprises a polyester resin and, as a crosslinking agent, a melamine resin and/or a benzoguanamine resin. This polyester resin is the one which can be obtained by polycondensing a polybasic carboxylic acid or its acid anhydride with a polyhydric alcohol in accordance with a conventional method. As the polybasic carboxylic acid or its acid anhydride, an aromatic polybasic carboxylic acid or a polybasic carboxylic acid comprising an aromatic polybasic carboxylic acid as the main component (more than 80 mol %), or its acid anhydride, is used in the present invention, so that the water resistance of the resulting coating film will be good. Specifically, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid or pyromellitic acid, and their anhydrides may be mentioned as typical examples.
In the present invention, an aliphatic or alicyclic polybasic carboxylic acid or its acid anhydride, such as adipic acid, succinic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, methylcyclohexene tricarboxylic acid, himic acid or cyclohexanedicarboxylic acid, or an anhydride thereof, may be used in combination with an aromatic polybasic carboxylic acid or its acid anhydride, in an amount of less than 20 mol %, preferably not more than 10 mol %, of the total polybasic carboxylic acid or its acid anhydride component. If it is used in combination in an amount of 20 mol % or more, the water resistance of the coating film tends to be poor, such being undesirable. If desired, a monocarboxylic acid such as benzoic acid may be incorporated in an amount of less than 2 mol % of the total polybasic carboxylic acid or its acid anhydride component.
In the present invention, as the polyhydric alcohol, a usual alcohol component for polyester, such as ethylene glycol, diethylene glycol, propanediol, neopentyl glycol, triethylene glycol, dipropylene glycol, butylene glycol, hexanediol, trimethylol propane, glycerol, sorbitol, pentanediol, octadecanediol or pentaerythritol may be used without any particular restriction. Glycidyl esters or glycidyl ethers may be used in combination with the polyhydric alcohol for modification.
With respect to the characteristic values of the polyester resin to be used in the present invention, the hydroxyl value is from 100 to 280, preferably from 120 to 250, and the acid value is from 0 to 15, preferably not higher than 10. Further, the weight average molecular weight is usually from 500 to 30,000, preferably from 1,000 to 10,000. If the hydroxyl value is lower than the above range, the affinity to water tends to be small, and the storage stability of the composition tends to be poor. Accordingly, a larger amount of an organic solvent is required. Further, crosslinking tends to be less during the curing, whereby the hardness or toughness of the coating film tends to be low. On the other hand, if the hydroxyl value is higher than the above range, the flexibility of the resulting coating film tends to be poor. Further, if the acid value is higher than the above range, the viscosity of the composition tends to be high, and the water resistance of the coating film thereby obtained tends to be low, such being undesirable.
In the present invention, a melamine resin having a triazine ring or a benzoguanamine resin having a triazine ring and an aromatic ring, is used as a crosslinking agent to improve the water resistance and hot water resistance of the coating film thereby obtained. Specifically, an alkyl-etherified melamine resin, an alkyl-etherified benzoguanamine resin, or an alkyl-etherified resin of diguanamine having two triazine rings bonded to a phenylene nucleus, may be mentioned as a typical example. In the present invention, a benzoguanamine resin having an aromatic ring and a triazine ring, is particularly preferred. A urea resin which is also an amino plasto resin, does not have a triazine ring and accordingly is inferior in the water resistance or hot water resistance, and it is not advisable to incorporate such a urea resin in a large amount. However, it is possible to incorporate such a urea resin in an amount of up to 15 wt % in the total crosslinking agent.
The binder component in the present invention comprises the polyester resin and the crosslinking agent, as described above. The blend ratio of the two is usually from 30:70 to 95:5, preferably from 40:60 to 80:20, as the weight ratio of the polyester resin to the crosslinking agent. If the polyester resin is less than this range, the crosslinking agent tends to react by itself, whereby the flexibility, chemical resistance, etc. of the coating film tend to deteriorate. On the other hand, if it is more than the above range, the crosslinking density tends to be low, whereby the water resistance, the hot water resistance, the solvent resistance, etc. tend to be low.
In the present invention, as the binder component, other resin such as an epoxy resin, a xylene resin or an acrylic resin may be used in combination as a part of the component.
In the present invention, as the solvent component constituting the water base coating composition, a solvent mixture comprising water and a hydrophilic organic solvent, is used. The hydrophilic organic solvent may, for example, be a solvent which is freely soluble in water at room temperature, such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, ethylene glycol, acetone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol or diethylene glycol monoethyl ether, or a solvent which is soluble in water at room temperature to some extent, such as sec-butanol, methyl ethyl ketone, ethyl formate, methyl acetate or propylene glycol monomethyl ether acetate. Such solvents may be used alone or in combination as a mixture of two or more of them. In addition to such a hydrophilic organic solvent, a small amount of a hydrophobic organic solvent such as mineral spirit, toluene or xylene may be incorporated.
The blend ratio of the water and the hydrophilic organic solvent varies depending upon the solid content of the water base coating composition, the hydroxyl value of the polyester resin, etc. However, the weight ratio of the water to the hydrophilic organic solvent is usually from 15:85 to 70:30, preferably from 20:80 to 55:45. If the amount of the organic solvent is less than this range, the storage stability under a high solid condition as an object of the present invention tends to be low. On the other hand, if it is more than the above range, the VOC value tends to be high, such being undesirable from the viewpoint of prevention of atmospheric pollution or conservation of resources.
The water base coating composition according to the first aspect of the present invention comprises the above described binder component and the solvent mixture as essential components, and may further contain various additives including a pigment such as a coloring pigment or an extender pigment, an acidic catalyst, a leveling agent, a defoaming and a lubricant, as the case requires.
With respect to the blend proportions of the respective components, the composition comprises from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight, of the pigment and from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of the additives, per 100 parts by weight of the binder component. The solvent mixture is incorporated so that the solid content of the water base coating composition would be from 50 to 80 wt %.
According to the second aspect, the present invention provides a water base coating composition having a pH of 6 to 10 and a solid content of from 50 to 80 wt % and having an epoxy phosphoric acid ester curing accelerator incorporated to the water base coating composition according to the first aspect of the present invention which comprises the above-mentioned binder component and the solvent mixture as the essential components and which may contain a pigment or additives, as the case requires.
The curing accelerator constituting the water base coating composition of the present invention can be produced, for example, by the following method. Namely, a phosphoric acid component such as orthophosphoric acid, a phosphoric acid condensate or pyrophosphoric acid is heat-reacted to an epoxy resin which preferably has an epoxy equivalent of from about 175 to 10,000, in the presence of a catalyst such as an imidazole or a phosphonium salt for triesterification or diesterification, followed by hydrolysis to obtain a monoesterified epoxy phosphoric acid ester resin curing accelerator.
Such a curing accelerator has a hydroxyl group and a phosphoric acid residue in its molecule and thus accelerate curing of the coating film and at the same time reacts with the binder to provide excellent crosslinking accelerating effects. Yet, it contributes to improvement of the adhesion and the corrosion resistance.
As a commercial product of such an epoxy phosphoric acid ester resin curing accelerator, XU-8096.07, XU-71899.00, XQ-82294.01 and DER621-EB50 (tradenames, manufactured by Dow Chemical Japan), Epototo ZX1300 and ZX1300-1 (tradenames, manufactured by Toto Kasei K. K.) may, for example, be mentioned.
The water base coating composition according to the second aspect of the present invention is required to have a pH of from 6 to 10, preferably a pH of from 7 to 9, so that the above-mentioned epoxy phosphoric acid ester resin curing accelerator is stably dissolved in the composition. For this purpose, as a neutralizing agent, an amine compound such as methylamine, diethylamine, trimethylamine, triethylamine, cyclohexylamine, diaminobenzene, ethylenimine, ethanolamine, dimethylethanolamine or diethanolamine, or ammonia may be used as a typical example. The water base coating composition according to the second aspect of the present invention comprises from 1 to 30 parts by weight, preferably from 5 to 20 parts by weight of the curing accelerator, from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight, of the pigment and from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of the additives, per 100 parts by weight of the above described binder component. Further, the solvent mixture is incorporated so that the solid content of the water base coating composition would be from 50 to 80 wt %.
The water base coating composition of the present invention is coated or printed on a substrate of a metal such as aluminum, stainless steel or steel, particularly preferably on an aluminum substrate, by a coating method such as roll coating, flow coating, spray coating or dip coating, or by a printing method such as gravure printing or screen printing, so that the dried film thickness would be from about 1 to 200 μm, preferably from 2 to 100 μm.
In the case of the water base coating composition according to the first aspect of the present invention, the coating film can be cured within a wide range of baking conditions ranging from baking at a temperature of from 100° to 200° C. for from 1 to 30 minutes to baking at a temperature of from 220° to 250° C. for a short period of time of a few tens seconds.
On the other hand, in the case of the water base coating composition according to the second aspect of the present invention, curing of the coating film is preferably conducted by baking at a temperature of from 150° to 200° C. for a short period of time of a few tens seconds, but it is possible to conduct baking at a baking temperature of not higher than 150° C. for a few minutes.
The water base coating composition of the present invention does not require neutralization of a resin of a high acid value with a neutralizing agent as required by a conventional water base coating composition and does not use an emulsifier or the like. Further, it uses an aromatic polybasic carboxylic acid as the acid component of the polyester resin and uses a crosslinking agent having a triazine ring, whereby the film thereby obtained is excellent in water resistance and hot water resistance. Further, it has a low VOC value and a high solid content, whereby it contributes to prevention of atmospheric pollution or conservation of resources. Further, its water content is little and thus has a feature that bubbling scarcely forms as compared with a conventional water base coating agent.
Further, when the epoxy phosphoric acid ester resin curing accelerator is incorporated, the composition will be excellent in low temperature curing in a short period of time without bringing about deterioration of the storage stability such as a viscosity increase, in addition to the above effects.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.
In the following Preparation Examples, Examples and Comparative Examples, "parts" and "%" mean "parts by weight" and "wt %", respectively.
Various components as identified in Table 1 were used in amounts (parts) as identified in Table 1, and polyester resin varnishes A to G were prepared in accordance with a conventional method under the conditions as identified in Table 1. The properties of the resins thus prepared are also shown in Table 1. In Table 1, "Carjular E" (tradename, manufactured by Yuka Shell Epoxy K. K.) is a synthetic fatty acidepichlorohydrin ester.
TABLE 1
__________________________________________________________________________
Polyester resin varnishes
A B C D E F G
__________________________________________________________________________
Amounts
Phthalic anhydride
40.0 20.0
40.0
40.0
40.0
33.3
(parts)
Isophthalic acid 44.7
22.4
of Trimellitic anhydride 14.4
compo-
Adipic acid 14.2
nents
Neopentyl glycol
27.4
21.4
27.4
33.8
14.6
27.4
28.0
Pentaerythritol
8.0 4.7 10.4
11.6
4.4 8.0 8.1
Carjular E 20.0
20.0
20.0
20.0
20.0
20.0
20.0
Xylene 5.0 5.0 5.0 5.0 4.0 5.0 5.0
Reaction
Temperature (°C.)
230 250 250 230 230 210 230
condi-
Time (hrs) 10 8 8 6 12 8 10
tions
Dilution
Diluted
Varnish viscosity
25 40 24 18 46 50 35
with (stokes
butyl
poise/20° C.)
cello-
Varnish solid
70 70 70 70 70 70 70
solve
content (%)
Resin
Weight average molecular
2300
3200
2300
2000
4600
4200
6000
proper-
weight
ties Hydroxyl value
240 120 280 360 60 180 210
Acid value 5 8 1 1 7 60 8
__________________________________________________________________________
Various components as identified in Table 2 were mixed in amounts (parts) as identified in Table 2 to obtain water base coating compositions. Each water base coating composition thus obtained was coated on a chromate-treated aluminum plate (thickness: 0.2 mm) by a roll coater so that the dried film thickness would be 8 μm, then set for 5 seconds and thereafter baked at 225° C. for 90 seconds. With respect to the coated plate thus obtained, tests for the hardness, the water resistance and the impact resistance were conducted, and the results are shown in Table 3.
Various components as identified in Table 2 were mixed in amounts (parts) as identified in Table 2, and adjusted to pH8 with methylamine (neutralizing agent) to obtain water base coating compositions. The properties of the water base coating compositions thus obtained are shown in Table 2. Each water coating composition thus obtained was coated on a chromate-treated aluminum plate (thickness: 0.2 mm) by a roll coater so that the dried film thickness would be 8 μm, then set for 5 seconds and thereafter baked at 200° C. for 60 seconds. With respect to the coated plate thus obtained, tests for the hardness, the water resistance and the impact resistance were conducted, and the appearance of the coating film was visually evaluated, and the results are shown in Table 3.
In Tables 2 and 3, "water-soluble polyester varnish" is "Water Sol S199-iM" (manufactured by Dainippon Ink and Chemicals, Inc.), solid content: 59%; "melamine resin (A)" is "Sumimal MC-1" (manufactured by Sumitomo Chemical Co., Ltd.), solid content 78%; "melamine resin (B)" is "Sumimal M40W" (manufactured by Sumitomo Chemical Co., Ltd.), solid content: 80%; "melamine resin (C)" is "Cymel 325" (manufactured by Mitsui Cyanamid K. K.), solid content: 100%; "benzoguanamine resin solution (A)" is "Mycoat 102" (manufactured by Mitsui Cyanamid K. K.), solid content: 70%; "benzoguanamine resin solution (B)" is "Mycoat 105" (manufactured by Mitsui Cyanamid K. K.), solid content: 70%; "urea resin solution" is "Yuban 10S" (manufactured by Mitsui Toatsu Chemical Co., Ltd.), solid content: 60%; "epoxy phosphoric acid ester resin curing accelerator" is "XQ-82294.01" (manufactured by Dow Chemical Japan), solid content: 50%; "bisphenol A type epoxy resin solution" is Epicoat #1001-70X (manufactured by Yuka Shell Epoxy K. K.), solid content: 70%, epoxy equivalent: 450 to 500; "VOC value" i.e. the amount of the volatile organic solvent in the coating material, is the value calculated by the following formula: ##EQU1## where, V, volatile content (wt %) in the coating material VW : water content (wt %) in the coating material
D: density of the coating material (25° C., g/ml)
DH2 O: density of water (25° C., 0.997 g/ml)
"Pencil hardness" is the value measured in accordance with JIS K5400; "water resistance" is the visual evaluation of the appearance of the coating film after immersion; "impact resistance" is tested by a Dupont system (1/2×300 gr×20 cm) and evaluated by O: no abnormality and X: abnormality such as cracking or peeling occurred; and "appearance of the coating film" is the visual evaluation of the appearance of the coating film and represented by O: no abnormality and X: bubbles observed.
TABLE 2
__________________________________________________________________________
Examples
1 2 3 4 5 6 7 8
__________________________________________________________________________
Amounts (parts) of constituting
components
Polyester resin varnish (A)
100 85.7 100 85.7
Polyester resin varnish (B)
85.7 78.6
Polyester resin varnish (C) 71.4 71.4
Polyester resin varnish (D)
Polyester resin varnish (E)
Polyester resin varnish (F)
Polyester resin varnish (G)
Water soluble polyester varnish
Melamine resin solution (A)
38.7 38.7
Melamine resin solution (B)
25 25 25 25
Melamine resin solution (C)
10 15
Benzoguanamine resin solution (A)
57.1 57.1
Benzoguanamine resin solution (B)
28.6 14.3
Urea resin solution
Epoxyphosphoric acid ester resin 20 15 10 30
curing accelerator
Bisphenol A type epoxy resin solution
14.3
14.3 7.1 7.1
Xylene
Mineral terpen 2 2
Butyl cellosolve 5.9 12.5 5
n-butanol
Water 16.0
17.8 13.5
16.2 17.5
17.3 20.0
9.7
Additives 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2
Properties of coating material
Non-volatile component (%)
62 62 63 64 62 61 61 63
Viscosity (Fordcup #4/25° C.) (sec)
95 90 98 87 95 90 98 87
VOC value 2.5 2.8 2.7 2.5 2.5 3.0 2.6 2.8
__________________________________________________________________________
Comparative Examples
1 2 3 4 5 6 7 8 9 10 11 12
__________________________________________________________________________
Amounts (parts) of constituting
components
Polyester resin varnish (A) 100 100
Polyester resin varnish (B)
Polyester resin varnish (C)
Polyester resin varnish (D)
100 100
Polyester resin varnish (E)
100 100
Polyester resin varnish (F)
71.4 85.7
Polyester resin varnish (G)
100 100
Water soluble polyester varnish 119 119
Melamine resin solution (A)
38.7
38.7
38.7
25.8 38.7
38.7
38.7
38.7 38.7
Melamine resin solution (B) 25
Melamine resin solution (C) 15
Benzoguanamine resin solution (A)
28.6
Benzoguanamine resin solution (B)
Urea resin solution 50 50
Epoxyphosphoric acid ester resin 20 20 20 10 20 20
curing accelerator
Bisphenol A type epoxy resin solution
14.3
Xylene 3 13.2
Mineral terpen 2 2
Butyl cellosolve 1.4
26.3
6.3
6.6
0.6 6
n-butanol 3.0 4
Water 15.4
3.7
13.6
16.3
10.0
71 12.0 15.5
20.0
9.1
71
Additives 1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
Properties of coating material
Non-volatile component (%)
64 58 62 60 62 43.6
64 64 62 60 61 44
Viscosity (Fordcup #4/25° C.) (sec)
87 90 81 105
85 90 87 90 81 105
85 90
VOC value 2.4
3.3
2.6
2.8
3.1
2.9
2.5
3.3
2.6
2.7
3.3
3.4
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
Examples
1 2 3 4 5 6 7 8
__________________________________________________________________________
Pencil hardness
Room temeprature
4H 4H 4H 5H 4H 4H 4H 5H
hardness
Hardness after immersion
HB 2H HB 2H 2H 2H 2H 2H
in hot water
of 90° C. for 30 minutes
Water resistance
Immersion at 20° C. for
No No No No No No No No
20 days abnor-
abnor- abnor-
abnor-
abnor-
abnor- abnor-
abnor-
mality
mality mality
mality
mality
mality mality
mality
Immersion at 90° C. for
No No No No No No No No
30 minutes abnor-
abnor- abnor-
abnor-
abnor-
abnor- abnor-
abnor-
mality
mality mality
mality
mality
mality mality
mality
Impact resitance
◯
◯
◯
◯
◯
◯
◯
◯
Appearance of the
◯
◯
◯
◯
◯
◯
◯
◯
coating material
__________________________________________________________________________
Comparative Examples
1 2 3 4 5 6 7 8 9 10 11 12
__________________________________________________________________________
Pencil hardness
Room temeprature
5H 3H 4H 4H H 2H 5H 3H 4H 4H H 2H
hardness
Hardness after immersion
4B 4B <6B 3B <6B 6B HB 4B <6B 3B <6B 6B
in hot water
of 90° C. for 30 minutes
Water resistance
Immersion at 20° C. for
No No No No No No No No
20 days abnor-
abnor-
abnor-
abnor-
abnor-
abnor-
abnor-
abnor-
mality
mality
mality
mality
mality
mality
mality
mality
Immersion at 90° C. for
Whiten-
Whiten-
No Whiten-
Whiten-
No Whiten-
Whiten-
No Whiten-
Whiten-
No
30 minutes ing ing abnor-
ing ing abnor-
ing ing abnor-
ing ing abnor-
mality mality mality mality
Impact resitance
X ◯
◯
◯
◯
◯
X ◯
◯
X ◯
◯
Appearance of the
◯
◯
◯
◯
◯
X ◯
◯
◯
◯
◯
X
coating material
__________________________________________________________________________
As is evident from the data in Table 3, in Examples 1 to 8 representing the water base coating composition of the present invention, excellent coating film properties were obtained.
On the other hand, among Comparative Examples 1 to 6 wherein no epoxy phosphoric acid ester resin curing accelerator was employed and Comparative Examples 7 to 12 wherein an epoxy phosphoric acid ester resin curing accelerator was employed, in the case of Comparative Examples 1 and 7 wherein a polyester resin having a large hydroxyl value was used, hot water resistance and the impact resistance were poor. In Comparative Examples 2 and 8 wherein a polyester resin having a small hydroxyl value was used, a large amount of an organic solvent was required to secure the stability of the coating material, whereby the VOC value tended to be high, and the hot water resistance was poor. In Comparative Examples 3 and 9 wherein an aliphatic polybasic carboxylic acid was used excessively, the hardness in hot water was low, the coating was susceptible to scratching. In Comparative Examples 4 and 10 wherein a polyester resin having a large acid value was used, the hot water resistance was poor. In Comparative Examples 5 and 11 wherein a urea resin was used as a crosslinking agent, the hot water resistance was poor. In Comparative Examples 6 and 12 wherein the amount of water was substantial as conventional water base coating compositions, bubbles were formed in the coating films when the setting time was short.
Claims (11)
1. A water base coating composition having a solid content of from 50 to 80 wt % and having a curable binder component dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said curable binder component comprising from 30 to 95 wt % of a crosslinkable polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and as a crosslinking agent from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
2. A water base coating composition having a solid content of from 50 to 80 wt % and having a curable binder component dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said curable binder component comprising from 30 to 95 wt % of a crosslinkable polyester resin obtained from a polybasic carboxylic acid or its acid anhydride comprising more than 80 mol % of an aromatic polybasic carboxylic acid or its acid anhydride and less than 20 mol % of an aliphatic or alicyclic polybasic alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and as a crosslinking agent from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
3. A water base coating composition having a pH of from 6 to 10 and a solid content of from 50 to 80 wt % and having a curable binder component and an epoxy phosphoric acid ester resin curing accelerator having a phosphoric acid residue and hydroxy group dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said curable binder component comprising from 30 to 95 wt % of a crosslinkable polyester resin obtained from an aromatic polybasic carboxylic acid or its acid anhydride and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and as a crosslinking agent from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
4. A water base coating composition having a pH of from 6 to 10 and a solid content of from 50 to 80 wt % and having a curable binder component and an epoxy phosphoric acid ester resin curing accelerator having a phosphoric acid residue and hydroxy group dissolved or dispersed in a solvent mixture comprising water and a hydrophilic organic solvent, said binder component comprising from 30 to 95 wt % of a crosslinkable polyester resin obtained from a polybasic carboxylic acid or its acid anhydride comprising more than 80 mol % of an aromatic polybasic carboxylic acid or its acid anhydride and less than 20 mol % of an aliphatic or alicyclic polybasic carboxylic acid or its acid anhydride, and a polyhydric alcohol and having a hydroxyl value of from 100 to 280 and an acid value of from 0 to 15, and as a crosslinking agent from 70 to 5 wt % of a melamine resin and/or a benzoguanamine resin.
5. The water base coating composition according to claim 3 or 4, wherein the epoxy phosphoric acid ester resin curing accelerator is incorporated in an amount of from 1 to 30 parts by weight per 100 parts by weight of the binder component.
6. The process of preparing a coated aluminum substrate which comprises coating the aluminum substrate with the water base coating composition of claim 1 and baking the coated substrate to cure the applied coating.
7. The process of preparing a coated aluminum substrate which comprises coating the aluminum substrate with the water base coating composition of claim 2 and baking the coated substrate to cure the applied coating.
8. The process of preparing a coated aluminum substrate which comprises coating the aluminum substrate with the water base coating composition of claim 3 and baking the coated substrate to cure the applied coating.
9. The process of preparing a coated aluminum substrate which comprises coating the aluminum substrate with the water base coating composition of claim 6 and baking the coated substrate to cure the applied coating.
10. The water base coating composition of claim 1 wherein the ratio of the water to the hydrophilic organic solvent is 15:85 to 70:30%.
11. The water base coating composition of claim 3 wherein the ratio of the water to the hydrophilic organic solvent is 15:85 to 70:30%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6068258A JPH07278490A (en) | 1994-04-06 | 1994-04-06 | Aqueous coating composition |
| JP6-068258 | 1994-04-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5608004A true US5608004A (en) | 1997-03-04 |
Family
ID=13368561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/416,983 Expired - Lifetime US5608004A (en) | 1994-04-06 | 1995-04-05 | Water base coating composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5608004A (en) |
| EP (1) | EP0676455B1 (en) |
| JP (1) | JPH07278490A (en) |
| CA (1) | CA2146210C (en) |
| DE (1) | DE69522131T2 (en) |
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| EP1310534A1 (en) * | 2001-11-07 | 2003-05-14 | Sigma Coatings S.A. | Treating primer for coil coating |
| JP2005307040A (en) * | 2004-04-22 | 2005-11-04 | Toyo Ink Mfg Co Ltd | COATING COMPOSITION AND METAL PLATE OR METAL CAN USING THE SAME |
| JP4919897B2 (en) * | 2007-07-24 | 2012-04-18 | トヨタ自動車株式会社 | Multi-layer coating formation method |
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- 1995-04-04 DE DE69522131T patent/DE69522131T2/en not_active Expired - Lifetime
- 1995-04-04 EP EP95105055A patent/EP0676455B1/en not_active Expired - Lifetime
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| US5412023A (en) * | 1989-12-06 | 1995-05-02 | Bollig & Kemper Kg | Aqueous dispersions of cross-linked polymer microparticles |
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| US12430453B2 (en) | 2021-02-02 | 2025-09-30 | Landa Corporation Ltd. | Mitigating distortions in printed images |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07278490A (en) | 1995-10-24 |
| CA2146210A1 (en) | 1995-10-07 |
| EP0676455A2 (en) | 1995-10-11 |
| DE69522131D1 (en) | 2001-09-20 |
| EP0676455A3 (en) | 1995-12-27 |
| DE69522131T2 (en) | 2002-04-25 |
| EP0676455B1 (en) | 2001-08-16 |
| CA2146210C (en) | 2006-07-18 |
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